Triazine thiol derivative having a perfluoro group, method for producing same and use of same

ABSTRACT

The triazine thiol derivative having a perfluoro group of the present invention is represented by the following chemical formula: ##STR1## in which &#34;n&#34; is an integer of 1-12, &#34;R&#34; is represented by the following general formula; 
     
         C.sub.m H.sub.2m+1 
    
     wherein m is an integer of 0-24, and M 1  and M 2  respectively represent H or an alkali metal. Such triazine thiol derivative having a perfluoro group is excellent in reactivity, solubility and surface activity.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel triazine thiol derivativehaving a perfluoro group, a method for producing the triazine thiolderivative, and a film for metal surface which is obtained by subjectinga metal to a surface treatment with use of the triazine thiolderivative.

2. Description of the Related Art

Triazine thiol derivatives have already been industrially manufactured(by some manufacturers such as Sankyo Kasei Co. Ltd.) and used ascrosslinking agents, adhesion accelerating agents, surface treatments,heavy metal treatments, anti-corrosive agents and the like. Among them,those triazine thiol derivatives whose substituent in 6 place isselected from the group consisting of --SH, --N(C₄ H₉)₂, --NHC₆ H₅ andmetal salts thereof have been especially used as surface treatments formetals and partly put to practical use (for example, "Practical SurfaceTreatment Techniques" by Mr. Ikuo Mori, 35, 595 (1988), "ChemicalIndustry" 42, 1005 (1991)). Although films of conventional triazinethiol derivatives provided on a surface of solid material such as ametal had large surface free energy, thereby attaining improved adhesionproperty, such conventional films were poor in anti-staining property,non-tackiness, anti-fogging property, lubricity and anti-icingperformance.

To solve the above-mentioned problems, Japanese Patent ApplicationLaid-Open No. 6-322595 discloses a method of manufacturing a metalmaterial in which triazine thiol compounds having perfluoro octylanilino group are electrodeposited on a solid material such as a metalby means of electrolytic polymerizing treatment, so that waterrepellency is imparted to the metal.

However, the triazine rings of the above-mentioned compounds are coupledby aromatic anilino group and thus, it has large cohesive force whilebeing an electron attractive group. Accordingly, the compounds are poorin solubility, low in reactivity of thiol group and further, criticalmicelle concentration (surface activity) of the compounds is high. As aresult, the above-mentioned compounds cannot perform the functions as asurface treatment agent for metals sufficiently, thereby greatlynarrowing the range of its practical use in industrial fields.

SUMMARY OF THE INVENTION

Under the circumstances stated above, the inventor has made variousstudies in order to solve the above problems and to attain a compoundhaving a novel molecular structure. As a result thereof, the presentinvention has been accomplished.

It is, therefore, an object of the present invention to provide atriazine thiol derivative having a perfluoro group, which is excellentin reactivity, solubility and surface activity so that it can impartproperties such as anti-staining property, nontackiness, anti-foggingproperty, release property, lubricity and anti-icing property to a metalsurface.

Another object of the present invention is to provide a method forefficiently and economically producing such triazine thiol derivativehaving a perfluoro group.

Still another object of the present invention is to provide apolymerized film of such triazine thiol derivative having a perfluorogroup which is formed on a metal surface by a dipping method,tribological method, or electrolytic polymerization method.

To accomplish the above-mentioned objects, there is provided accordingto the present invention, a triazine thiol derivative having a perfluorogroup represented by the following chemical formula (1): ##STR2##wherein "n" is an integer of 1-12, "R" is represented by the followinggeneral formula;

    C.sub.m H.sub.2m+1

wherein m is an integer of 0-24, and M₁ and M₂ respectively represent ahydrogen atom (H) or an alkali metal.

The present invention also provides a method for producing a triazinethiol derivative having a perfluoro group comprising preparation stepsof:

(1) synthesizing a secondary amine having a perfluoro group;

(2) synthesizing a triazine dichloride having a perfluoro group from thesecondary amine having a perfluoro group and a cyanur chloride; and then

(3) synthesizing a triazine thiol derivative having a perfluoro groupfrom the triazine dichloride having a perfluoro group.

In such method for producing a triazine thiol derivative having aperfluoro group, the secondary amine having a perfluoro group may beprepared through a reaction represented by the following reactionformula (2); ##STR3## the triazine dichloride having a perfluoro groupmay be prepared through a reaction represented by the following reactionformula (3); ##STR4## and the triazine thiol derivative having aperfluoro group may be prepared through a reaction represented by thefollowing reaction formula (4); ##STR5##

The present invention further provides a film for metal surfacecomprising the triazine thiol derivative having a perfluoro group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will be described in detail with reference topreferred embodiments.

A triazine thiol derivative having a perfluoro group according to thepresent invention is represented by the following chemical formula (1):##STR6##

In the above formula, "R" is represented by the following generalformula;

    C.sub.m H.sub.2m+1

wherein m is an integer of 0-24, and depending on the purpose of use,"R" may be longer or shorter than the perfluoro group. Especially in thecase where "R" is --C₃ H₇, --C₄ H₉, --C₁₂ H₂₅ or --C₁₈ H₃₇, theresulting product is often excellent in solubility. When "R" is longerthan the perfluoro group, the resulting product effectively functions insuch case where a polymeric material of fluorocarbon and olefin aremiscibilized in the interface. On the other hand, when "R" is shorterthan the perfluoro group, the resulting triazine thiol derivative issuitable for treatments such a surface treatment agent which arerequired to display the properties of fluorine.

In the perfluoro group --CH₂ C_(n) F₂₊₁ in the above-mentioned formula(1) in which "n" is an integer of 1-12, the amount of "n" influences thedisplay of fluorine properties. The "n" may preferably be an integerbetween 1 to 12 from the view point of the balance between fluorineproperties and solubility. Among them, --CH₂ C₉ F₁₉ is especiallyeffective. When the perfluoro group is shorter than the above-mentionedrange, the properties of fluorine cannot be displayed sufficiently. Onthe other hand, when the amount of "n" is larger than the above range,the resulting product involves such problems that solubility of rawmaterials decreases and synthesis of materials becomes difficult inspite of increased display of fluorine properties.

When M₁ and M₂ in the above formula (1) are respectively an H (in thiscase, the substance may be referred to as a triazine thiol having aperfluoro group), the triazine thiol having a perfluoro group may beeffectively used when it is dissolved in an organic solvent such astetrahydrofuran, dimethylformamide, glycols, pyrolidone, dimethylsulfoxide, ketons and the like.

In the case where both or either of M₁ and M₂ in the above formula (1)is an alkali metal, for example both or either of M₁ and M₂ is Li, Na, Kor Ce, the triazine thiol derivative having a perfluoro group isdissolved in water, alcohol, or a mixed solvent thereof for thepractical use.

When both or either of M₁ and M₂ in the above formula (1) is an ammoniaor an amine such as ethanolamines, alkylamines and the like, theresulting triazine thiol derivative having a perfluoro group is used inthe form of paste.

The above-described triazine thiol derivative having a perfluoro groupaccording to the present invention is excellent in reactivity,solubility and surface activity when compared with the conventionalfluorinated triazine thiol.

The triazine thiol derivative having a perfluoro group according to thepresent invention, which is represented by the above-mentioned formula(1), can be produced through the following three steps:

(1) synthesizing a secondary amine having a perfluoro group;

(2) synthesizing a triazine dichloride having a perfluoro group from thesecondary amine having a perfluoro group and a cyanur chloride; and then

(3) synthesizing a triazine thiol derivative having a perfluoro groupfrom the triazine dichloride having a perfluoro group.

A typical synthetic reaction of the above-mentioned secondary aminehaving a perfluoro group is as follows: ##STR7## wherein Rf isrepresented by the general formula:

    --CH.sub.2 C.sub.n F.sub.2n+1

and n is an integer of 1-12.

For example, a perfluorocarboxylic acid is reacted with SO₂ Cl₂ underthe presence of pyridine to prepare a perfluorocarboxylic chloride (1-1)and then, the thus-obtained perfluorocarboxylic chloride is reacted withammonia or a primary amine, thereby obtaining a perfluoro carboxylicamide (1-2). In place of the above-mentioned perfluorocarboxylicchloride, a perfluoro carboxylic halide such as a perfluoro carboxylicfluoride or the like. After that, the thus-obtained perfluoro carboxylicamide is reduced in a solvent of ethers, in which LiAlH₄, B₂ H₆, NaBH₄,ZnCl₂, CoCl₂ or the like is coexistent, thereby synthesizing a secondaryamine having a perfluoro group (1-3).

Next, a typical reaction between the above-explained secondary aminehaving a perfluoro group and a cyanur chloride is shown in the formula(3) below: ##STR8##

In the reaction represented by the above formula (3), the triazinedichloride having a perfluoro group is obtained as follows. First, acyanur chloride is dissolved in an organic solvent such as acetone,tetrahydrofuran, dioxane, alcohols, and the like at a temperature of 0°C. or lower, and a solution of the secondary amine having a perfluorogroup, which is obtained in the reaction represented by the aboveformula (2), is dropped thereto. The moment when the solution of thesecondary amine having a perfluoro group is dropped, the temperature ofthe reaction solution increases, whereby the reaction begins. In thisconnection, the reaction temperature may preferably be maintained withinthe range of 0-5° C. from the view point of preventing a side reaction.After finishing the dropping of the solution of the secondary aminehaving a perfluoro group, the reaction solution is stirred for 60minutes and then, an aqueous solution of Na₂ CO₃ is dropped thereto.Just like the case when the solution of the secondary amine having aperfluoro group is dropped, it is confirmed that the reactiontemperature is raised due to the dropping of Na₂ CO₃. Also in this case,the reaction temperature should be maintained within the range of 0-5°C. while stirring and dropping are continued. Then, the reaction mixtureis poured into water or washed with water after distilling off thesolvent, thereby obtaining a crude triazine dichloride having aperfluoro group.

A typical synthetic reaction of a triazine thiol derivative having aperfluoro group is shown in the following formula (4): ##STR9##

Specifically, the triazine dichloride having a perfluoro group obtainedin the above reaction is reacted with a soda hydrosulfide of 3 mol inalcohol or dimethylformamide to attain a triazine thiol derivativehaving a perfluoro group of the present invention. The above formula (4)represents a typical thiolating method, and a soda sulfide or alkalisulfide may be used in place of a soda hydrosulfide.

Further, an indirect thiolating method can be carried out with use of analkaline carbamate or an alkali metal xanthate and, through a reactionbetween the product thereof and a secondary amine, there can be obtaineda triazine thiol derivative having a perfluoro group according to thepresent invention.

The triazine thiol derivative having a perfluoro group according to thepresent invention may form a film comprising a perfluoro group on ametal surface by a dipping method, tribological method, or electrolyticpolymerization method, thereby providing the metal surface withproperties such as anti-staining property, non-tackiness, anti-foggingproperty, lubricity and anti-icing property.

In a dipping method, a film is formed on a metal such as a copper,copper alloy, nickel, iron, aluminum and the like by dipping such metalin an aqueous solution or organic solution of the triazine thiolderivative having a perfluoro group for 0.1-120 minutes, preferably for3-30 minutes. In this case, the concentration of the solution of thetriazine thiol derivative having a perfluoro group is within the rangeof 0.001-5 weight %, preferably within the range of 0.01-1 weight %. Theoptimum value of concentration varies depending on the kind of metal tobe dipped, dipping temperature and dipping time.

A suitable dipping temperature differs with the concentration of thesolution, the kind of metal, especially with the solvent to be used andtherefore, it is impossible to specify a single optimum value for thedipping temperature. In the case of an aqueous solution, it cangenerally vary from 1° C. to 99° C., and desirably the dippingtemperature is within the range of 20° C.-80° C. By this dipping method,a uniform film can be formed on a metal product which has a complicatedshape. However, the thus-formed film is low in strength because it is amonomer film. Accordingly, after the dipping, the monomer film may besubjected to heating at a temperature of 100° C. or higher, so that itturns into a polymer film. The dipping method described above isespecially suitable for a surface treatment of a copper and copperalloy.

In a tribological polymerization method, the triazine thiol derivativehaving a perfluoro group dissolved or mixed in a water based lubricantor an oil based lubricant, or alternatively, the triazine thiolderivative having a perfluoro group by itself is used as a lubricantduring a machining process of a metal such as elongation, cutting, wiredrawing and forging, thereby simultaneously conducting the machining anda surface treatment of the metal. Processing machines for elongation,cutting, wire drawing and forging are not limited to particular types aslong as they are ordinarily used ones. During the above-mentionedmachining processes, the metal momentarily produces a high heat, formsan active new surface and discharges exo-electrons. As a result, thetriazine thiol derivative having a perfluoro group in contact with thelubricant are polymerized, thereby forming a film on the metal surface.When the triazine thiol derivative having a perfluoro group of thepresent invention is dissolved or mixed in a lubricant which ispresently available for use, the concentration of resulting dissolutionor mixture is generally within a range of 0.001-5 weight %, preferablywithin a range of 0.01-1 weight %. It is needless to say that even whenit is difficult to dissolve the triazine thiol derivative having aperfluoro group in a certain lubricant, the aim also can be accomplishedby mixing and slightly dispersing the triazine thiol derivative having aperfluoro group in the lubricant.

In an electrolytic polymerization method, a film of the triazine thiolderivative having a perfluoro group is formed on a surface of a metal oran electric conductor by an electrolytic method such as a cyclic method,a constant-current method, a constant-potential method, a pulseconstant-potential method, a pulse constant-current method and the like,wherein an electrolysis is conducted in an aqueous solution or anorganic solution of the triazine thiol derivative having a perfluorogroup, which also includes an electrolyte, with use of an anode of ametal to be treated and a cathode of a platinum plate or a stainlesssteel plate. Metals to be treated in this method are not restricted aslong as the metals have electrical conductivity. As examples of suchmetals, mention would be made of iron, iron alloy (such as stainlesssteel, and permalloy), copper, copper alloy, nickel, gold, silver,platinum, cobalt, aluminum, zinc, lead, tin, tin alloy, titanium, chromeand the like. The above-mentioned electric conductor may include aconductive film, ITO, carbon, conductive rubber, organic conductor andthe like.

The above-mentioned electrolyte are not limited to particular materialsas long as it has solubility to a solvent used, electric conductivity aswell as stability. In general, NaOH, Na₂ CO₃, Na₂ SO₄, K₂ SO₃, Na₂ SO₃,K₂ SO₃, NaNO₂, KNO₂, NaNO₃, NaClO₄, CH₃ COONa, Na₂ B₂ O₇, NaH₂ PO₂,(NaPO₃)₆, Na₂ MoO₄, Na₃ SiO₃ and the like are suitably used as anelectrolyte. The concentration of these electrolyte is generally withina range of 0.001-1mol/L, preferably within a range of 0.1-0.5 mol/L fromthe view point of the growth rate of the film.

As the above-described solvent, one which can dissolve an electrolyteand the triazine thiol derivative having a perfluoro group at the sametime is desirable and combination of such solvents is not particularlyrestricted. As examples of such solvent, mention may be made of water,methanol, ethanol, carbitol, Cellosolve, dimethylformamide,methylpyrolidone, acrylnitrile, ethylene carbonate and the like.

The concentration of the triazine thiol derivative having a perfluorogroup is within the range of 0.01-100 mmol/L, preferably within therange of 0.1-10 mmol/L. The temperature of the electrolyte differs withthe freezing point and boiling point of the solvent used and therefore,it is difficult to specify a single optimum value for the temperature ofthe electrolyte. For example, in the case of an aqueous solution, thetemperature varies from 1° C. to 99° C., but it is within the range of20° C.-80° C.

As the material for the counter electrode (the cathode), a discretionalmaterial can be used as long as it neither reacts with the electrolytenor has extremely low conductivity. In general, an inactive electricconductor such as a stainless steel, platinum, carbon and the like isused as the counter electrode.

The cyclic method is conducted with such a potential width that thesolvent is not decomposed. Such potential width cannot be specificallyrestricted since it is affected by the kinds of solvent and electrolyteto be used. The constant-potential method is conducted at a potentialwithin the range of -0.5-2 V vs. CES, preferably at a potential withinthe range from a spontaneous potential to an oxidation potential. Whenconstant-potential method is conducted at a potential lower than thespontaneous potential, there is such a risk that no polymerizationoccurs. On the other hand, constant-potential method at a potentialhigher than the oxidation potential takes a risk of decomposition of thesolvent.

In the constant-current method, a suitable current density is within therange of 0.005-50 mA/cm², preferably within the range of 0.05-5 mA/cm².When the current density is lower than 0.05 mA/cm², growth of a filmtakes too long time. When the current density is higher than 5 mA/cm²,there may happen such an undesirable phenomenon that a crack appears inthe resulting film or the metal elutes into the electrolyte.

In a pulse method, an electrolytic potential and an electrolytic currentdensity may be decided just as described above, and the duration ofelectrolysis is within the range of 0.01-10 minutes, preferably withinthe range of 0.1-2 minutes. When the duration is shorter than 0.01minute or longer than 10 minutes, the effects of the pulse method cannotbe attained sufficiently.

With respect to preliminary treatments of a metal, a foreign substancesuch as an organic substance should be removed from the metal surface.However, substances such as oxides do not matter as long as they do notconsiderably deteriorate the conductivity. An activating treatment isnot necessary as long as conductivity of the metal is not considerablydeteriorated.

The following examples and comparative examples are given inillustration of the present invention and are not intended aslimitations thereof.

EXAMPLES 1-10

After adding a perfluoro alkyl carboxylic acid (0.50 mol) and adimethylformamide (DMF) into hexane (200 ml), a thionyl chloride (1 mol)was dropped thereinto and the resulting solution was heated at refluxfor 24 hours. The solvent and the excess of thionyl chloride wereremoved by means of an evaporator and then, distillation was conductedunder a reduced pressure, thereby obtaining a perfluoro alkyl carboxylicchloride. The thus-obtained perfluoro alkyl carboxylic chloride waspurified by further conducting the reduced-pressure distillation twice.The yield was 45-89%.

In the case of a perfluoro alkyl carboxylic acid having a carbon numberof not more than 4, a phosphorus pentachloride and toluene were used,and the reaction was conducted at 50° C. for 24 hours. An initialdistillate obtained by distilling this reaction solution was a perfluoroalkyl carboxylic chloride. The thus-obtained perfluoro alkyl carboxylicchloride was purified by conducting the distillation again. The yieldwas 45-62%.

Then, a triazine thiol derivative having a perfluoro group wassynthesized through the processes represented by formulae (1-1), (1-2)and (1-3) of the chemical formula (2), formula (2-1) of the chemicalformula (3) and formula (3-1) of the chemical formula (4).

Characteristic values of a perfluoro alkyl amine, 6-perfluoroalkylamino-1,3,5-triazine-2,4-dichloride and 6-perfluoroalkylamino-1,3,5-triazine-2,4-dithiol obtained in Examples 1-10 arerespectively shown in Tables

                                      TABLE 1                                     __________________________________________________________________________    Characteristic values of perfluoro alkyl amine                                                         Distillation                                                                        Melting IR characteristic                           Amine including                                                                           Yield   boiling point                                                                       point                                                                              N.sup.1)                                                                         absorption.sup.2)                      Example                                                                            fluorine    (%)                                                                              State                                                                              (° C./Torr)                                                                  (° C.)                                                                      (%)                                                                              (cm.sup.-1)                            __________________________________________________________________________    1    CF.sub.3 (CF.sub.2)CH.sub.2 NH.sub.2                                                      84 colorless/                                                                         49-50/                                                                              --   9.4/                                                                             NH: 3312w, 31924w                                          liquid                                                                             760        9.39                                                                             CH: 2958m, 2878m                                                              CF: 1209s, 1149s                       2    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH.sub.2                                               53 colorless/                                                                         79-82/                                                                              --   3.6/                                                                             NH: 3312w, 31924w                                          liquid                                                                             32         3.51                                                                             CH: 2958m, 2878m                                                              CF: 1209s, 1149s                       3    CF.sub.3 (CF.sub.2).sub.8 CH.sub.2 NH.sub.2                                               45 colorless/                                                                         95-99/                                                                              43-44                                                                              2.7/                                                                             NH: 3420w, 3215w                                           solid                                                                              15         2.81                                                                             CH: 2952m, 2872m                                                              CF: 1245s, 1205s, 1149s                4    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NHC.sub.4 H.sub.7                                      72 colorless/                                                                         recrystal-                                                                          104-105                                                                            3.0/                                                                             NH: 3241w, 3216w                                           solid                                                                              lized      3.09                                                                             CH: 2950m, 2871m                                                              CF: 1245s, 1204s, 1150s                5    CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 NH.sub.2                                               79 colorless/                                                                         39-40/                                                                              --   2.7/                                                                             NH: 3367w                                                  liquid                                                                             0.3        2.55                                                                             CH: 2966m, 2862m                                                              CF: 1242s, 1210s, 1150s                6    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NHC.sub.8 H.sub.17                                     59 colorless/                                                                         40-84/                                                                              --   2.8/                                                                             NH: 3375w                                                  liquid                                                                             0.07       2.64                                                                             CH: 2931m, 2860m                                                              CF: 1242s, 1211s, 1150s                7    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NHC.sub.12 H.sub.25                                    74 colorless/                                                                         113-118/                                                                            --   2.4/                                                                             NH: 3346w                                                  liquid                                                                             0.07       2.47                                                                             CH: 2928m, 2857m                                                              CF: 1243s, 1211s, 1150s                8    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NHC.sub.6 H.sub.5                                      93 colorless/                                                                         78-79/                                                                              41-42                                                                              3.0/                                                                             NH: 3417w                                                  solid                                                                              0.3        2.95                                                                             CH: 3058w, 1606m                                                              CF: 1232s, 1200s, 1144s                9    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NHC.sub.6 H.sub.11                                     82 colorless/                                                                         65-68/                                                                              --   2.8/                                                                             NH: 3443w                                                  liquid                                                                             0.3        2.91                                                                             CH: 2935m, 2860m                                                              CF: 1241s, 1209s, 1150s                10   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 NHC.sub.4 H.sub.7                                      41 colorless/                                                                         41-43/                                                                              --   2.3/                                                                             NH: 33469w                                                 liquid                                                                             0.3        2.32                                                                             CH: 2930m, 2859m                                                              CF: 1243s, 1211s,                      __________________________________________________________________________                                           1150s                                   .sup.1) Analyzed by Kjeldahl method; upper row: observed value; lower row     calculated value                                                              .sup.2) w: weak peak strength; m: medium peak strength; s: strong peak        strength                                                                 

                                      TABLE 2                                     __________________________________________________________________________    Characteristic values of 6-perfluoro alkylamino-1,3,5-triazine-2,4-dichlor    ide                                                                                               Melting    IR characteristic                                               Yield                                                                            point                                                                              N.sup.1)                                                                         C.sup.1)                                                                         absorption.sup.2)                              Example                                                                            Substituent in 6 place                                                                    (%)                                                                              (° C.)                                                                      (%)                                                                              (%)                                                                              (cm.sup.-1)                                    __________________________________________________________________________    1    CF.sub.3 (CF.sub.2)CH.sub.2 NH--                                                          90 84-85                                                                              18.6/                                                                            23.6/                                                                            NH: 3247w, CH: 2947m                                                    18.87                                                                            23.87                                                                            --N═N<: 1587s, 1524m                                                      CF: 1235s, 1201s, 1144s                        2    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH--                                                   89 89-90                                                                              10.3/                                                                            12.8/                                                                            NH: 3286w, CH: 2947m                                                    10.24                                                                            12.96                                                                            --N═C<: 1596s, 1523m                                                      CF: 1209s, 1149s                               3    CF.sub.3 (CF.sub.2).sub.8 CH.sub.2 NH--                                                   75 98--99                                                                             8.8/                                                                             10.5/                                                                            NH: 3274w, CH: 3138m                                                    8.66                                                                             10.95                                                                            --N═C<: 1612s, 1553m                                                      CF: 1252s, 1211s, 1150s                        4    CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 NH--                                                   49 102-103                                                                            7.9/                                                                             8.7/                                                                             NH: 3264w, CH: 3118m                                                    8.04                                                                             8.94                                                                             --N═C<: 1615s, 1559m                                                      CF: 1258s, 1211s, 1150s                        5    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                   87 144-145.sup.3) /                                                                   9.5/                                                                             11.9/                                                                            CH: 2967m, 2879m                                                   1    9.32                                                                             11.79                                                                            --N═C<: 1560s, 1493m                                                      CF: 1242s, 1211s, 1149s                        6    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.8 H.sub.17)N--                                  71 144-147.sup.3) /                                                                   8.6/                                                                             10.7/                                                                            CH: 2957m, 2860m                                                   0.2  8.50                                                                             10.75                                                                            --N═C<: 1558s, 1494m                                                      CF: 1243s, 1211s, 1150s                        7    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.12 H.sub.25)N--                                 67 160-162.sup.3) /                                                                   7.9/                                                                             10.0/                                                                            CH: 2929m, 2858m                                                   0.1  7.83                                                                             9.91                                                                             --N═C<: 1560s, 1493m                                                      CF: 1243s, 1211s, 1150s                        8    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.5)N--                                   55 75-76                                                                              9.2/                                                                             11.2/                                                                            CH: 3068m, 1612m                                                        8.99                                                                             11.38                                                                            --N═C<: 1559s, 1491m                                                      CF: 1243s, 1211s, 1150s                        9    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                  77 60-61                                                                              8.7/                                                                             11.4/                                                                            CH: 2935w, 2860m                                                        8.91                                                                             11.27                                                                            --N═C<: 1561s, 1492m                                                      CF: 1245s, 1207s, 1147s                        10   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                   65 55-65                                                                              7.6/                                                                             9.7/                                                                             CH: 2967w, 2879m                                                        7.46                                                                             9.44                                                                             --N═C<: 1560s, 1493m                                                      CF: 1244s, 1210s, 1149s                        __________________________________________________________________________     .sup.1) Analyzed by Kjeldahl method; upper row: observed value; lower row     calculated value                                                              .sup.2) w: weak peak strength; m: medium peak strength; s: strong peak        strength                                                                      .sup.3) upper row: distillation temperature (° C.); lower row:         degree of vacuum (Torr)                                                  

EXAMPLES 11-18

Solubility of 6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol tovarious solvents are shown in Table

                                      TABLE 3                                     __________________________________________________________________________    Characteristic values of 6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol                      Melting       IR characteristic                                               point   SH.sup.2)                                                                        N.sup.2)                                                                         absorption.sup.3)                             Example                                                                            Substituent in 6 place                                                                     (° C.)                                                                      UV.sup.1)                                                                        (%)                                                                              (%)                                                                              (cm.sup.-1)                                   __________________________________________________________________________    1    CF.sub.3 (CF.sub.2)CH.sub.2 NH--                                                           146-148                                                                            227/                                                                             22.5/                                                                            192/                                                                             NH: 3245w, CH: 2946m                                                 2.81                                                                             22.63                                                                            19.17                                                                            --NHCS--: 1595s, 1523m                                                        CF: 1197s, 1157s                              2    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH--                                                    246-248                                                                            296/                                                                             12.3/                                                                            10.1/                                                                            NH: 32067w, CH: 2946m                                                2.96                                                                             12.19                                                                            10.33                                                                            --NHCS--: 1592s, 1523m                                                        CF: 1209s, 1148s                              3    CF.sub.3 (CF.sub.2).sub.8 CH.sub.2 NH--                                                    --   270/                                                                             9.9/                                                                             9.1/                                                                             NH: 3274w, CH: 3120m                                                 2.83                                                                             10.30                                                                            8.72                                                                             --NHCS--: 1633s, 1581m                                                        CF: 1236s, 1208s, 1150s                       4    CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 NH--                                                    --   270/                                                                             9.6/                                                                             7.9/                                                                             NH: 3261w, CH: 3120m                                                 2.77                                                                             9.56                                                                             8.09                                                                             --NHCS--: 1616s, 1558m                                                        CF: 1248s, 1207s, 1150s                       5    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                    217-219                                                                            270/                                                                             11.2/                                                                            9.1/                                                                             CH: 2965m 2879m                                                      2.83                                                                             11.05                                                                            9.36                                                                             --NHCS--: 1593s, 1495m                                                        CF: 1242s, 1211s, 1149s                       6    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.8 H.sub.17)N--                                   146-148                                                                            270/                                                                             10.3/                                                                            8.7/                                                                             CH: 2931m, 2861m                                                     2.81                                                                             10.11                                                                            8.56                                                                             --NHCS--: 1591s, 1496m                                                        CF: 1278s, 1207s, 1149s                       7    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (CH.sub.12 H.sub.25)N--                                 117-118                                                                            270/                                                                             9.4/                                                                             7.8/                                                                             CH: 2928m, 2857m                                                     2.77                                                                             9.31                                                                             7.89                                                                             --NHCS--: 1588s, 1498m                                                        CF: 1238s, 1200s, 1143s                       8    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.5)N--                                    125-127                                                                            285/                                                                             10.9/                                                                            9.3/                                                                             CH: 3068m, 1612m                                                     2.89                                                                             10.70                                                                            9.06                                                                             --NHCS--: 1558s, 1494m                                                        CF: 1243s, 1211s, 1150s                       9    CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                   119-120                                                                            270/                                                                             10.2/                                                                            8.8/                                                                             CH: 2942m, 2866m                                                     2.84                                                                             10.59                                                                            8.97                                                                             --NHCS--: 1576s, 1535m                                                        CF: 1245s, 1207s, 1147s                       10   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                    223-224                                                                            270/                                                                             8.8/                                                                             7.5/                                                                             CH: 2937m, 2859m                                                     2.74                                                                             8.86                                                                             7.51                                                                             --NHCS--: 1588s, 1539m                                                        CF: 1242s, 1212s, 1150s                       __________________________________________________________________________     .sup.1) upper row: peak wavelength (nm); lower row: ×10.sup.-4          (mol/L)                                                                       .sup.2) upper row: observed value; lower row: calculated value (N and SH      were respectively analyzed by Kjeldahl method and AgVolhalt method.           .sup.3) w: weak peak strength; m: medium peak strength; s: strong peak        strength                                                                 

                                      TABLE 4                                     __________________________________________________________________________    Solubility of 6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol                                Solvents                                                     Example                                                                            Substituent in 6 place                                                                    Water                                                                             Ethanol                                                                           Toluene                                                                           Acetic ether                                                                        MEK                                        __________________________________________________________________________    11   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH--                                                   ◯                                                                     ◯                                                                     Δ                                                                           Δ                                                                             ◯                              12   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                   ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                       ⊚                           13   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                  ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                       ⊚                           14   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                   ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                       ⊚                           Compar-                                                                            CF.sub.3 (CF.sub.2).sub.6 C.sub.6 H.sub.4 NH--                                            Δ                                                                           Δ                                                                           X   Δ                                                                             Δ                                    ative                                                                         example                                                                       __________________________________________________________________________     X: did not solved;                                                            Δ: slightly solved (1 wt % or less);                                    ◯: sufficiently solved (1-10 wt %);                               ⊚: excellently solved (10 wt % or more)                   

As seen from the above Table 4, all examples of the present inventionhave higher solubility than the comparative example, becausesubstituents of examples have a higher flexing property than that of thecomparative example. Accordingly, it is understood that the triazinethiol derivative having a perfluoro group of the present invention iseffective as a surface treating agent.

In Table 5 below, there is shown the effectiveness of 6-perfluoroalkylamino-1,3,5-triazine-2,4-dithiol of examples of the presentinvention by comparing the dissociation constants, oxidation potentialand critical micelle concentration with those of the comparativeexample.

                                      TABLE 5                                     __________________________________________________________________________    Dissociation constant, oxidation potential and critical micelle               concentration of                                                              6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol                                                           Critical                                                               Oxidation                                                                            micelle                                                                potential                                                                            concentration                                   Example                                                                            Substituent in 6 place                                                                    pKa1                                                                             pKa2                                                                             (V vs. Ag.sup.+ /Ag)                                                                 (mol/L)                                         __________________________________________________________________________    15   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH--                                                   8.1                                                                              10.3                                                                             0.62   2.1 × 10.sup.-3                           16   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                   7.4                                                                              10.4                                                                             0.46   2.1 × 10.sup.-5                           17   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                  6.2                                                                              10.6                                                                             0.78   5.6 × 10.sup.-5                           18   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                   7.5                                                                               9.8                                                                             0.56   1.1 × 10.sup.-5                           Compar-                                                                            CF.sub.3 (CF.sub.2).sub.6 C.sub.6 H.sub.4 NH--                                            8.3                                                                              10.7                                                                             0.90   2.2 × 10.sup.-2                           ative                                                                         example                                                                       __________________________________________________________________________

With respect to the dissociation constants (pKa₁, pKa₂), which mayfunction as a yardstick for reactivity, all the examples of the presentinvention have lower dissociation constants than the comparativeexample. Accordingly, it is understood that the triazine thiolderivative having a perfluoro group of the present invention has anexcellent reactivity. With regard to the oxidation potential whichfunctions as a yardstick for easiness of tribological polymerization andelectrolytic polymerization, each example has a lower oxidationpotential than the comparative example. This means that an oxidativepolymerization of the triazine thiol derivative having a perfluoro groupaccording to the present invention is easier than that of thecomparative example. Further, the critical micelle concentration ofevery example is lower than that of the comparative example. This meansthat micelle formation is easier in the examples and thus, the triazinethiol derivative having a perfluoro group according to the presentinvention has an excellent surface activity. Since it is assumed thatthose substances which have excellent surface activity has moreregularly arranged molecules in the resulting products, it is suggestedthat a film of the triazine thiol derivative having a perfluoro groupaccording to the present invention is minute and thus, excellent incorrosion resistance.

EXAMPLES 19-22

Dipping Treatment

An Na salt of each 6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiolshown in Table 6 below was dissolved in water at a concentration of1×10⁻³ mol/L and then, a plate (3×6×0.2 mm) of iron, copper, nickel andsilver (silver coated plate) were dipped therein at 70° C. for 30minutes. In this connection, these metals were subjected to preliminarytreatment by conducting ultrasonic degreasing for 3 minutes intrichloroethylene to remove deposits and the like, and kept in newtrichloroethylene until the actual use. Surface treating performancewith respect to each metal was evaluated though a contact angle of waterand an eluting potential of the metal which was obtained from the anodicpolarization curve [electrolyte: an aqueous solution of (NaPo₃)₆ of 0.1M]. The results are also shown in Table 6. The contact angle showswhether water repellency was given to the metal surface and, the elutionpotential functions as a yardstick for thickness and corrosionresistance of a film formed on each metal. The larger contact angleindicates the higher water repellency, and the higher elution potentialmeans the thicker film with superior corrosion resistance. Althougheffects of the fluorine group are seen in both of examples 19-22 and thecomparative example, the examples of the present invention exhibitedgreater effects in both contact angle and elution potential than thecomparative example. Accordingly, it is said that the reactivity with ametal surface as well as the thickness of a formed film of the examplesare superior to those of the comparative example.

                                      TABLE 6                                     __________________________________________________________________________    Dipping treatment of metals with use of                                       6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol                                              Evaluated                                                    Example                                                                            Substituent in 6 place                                                                    Property                                                                              Iron                                                                             Copper                                                                            Nickel                                                                            Silver                                    __________________________________________________________________________    19   CF.sub.3 (CF.sub.2).sub.5 CH.sub.2 NH--                                                   Contact angle (°)                                                              113                                                                              121 117 121                                                                (56)                                                                             (67)                                                                              (82)                                                                              (68)                                                       Eluting potential                                                                     1.5                                                                              1.7 1.75                                                                              1.1                                                        (V vs SCE)                                                                            (1.4)                                                                            (-0.2)                                                                            (1.5)                                                                             (0.3)                                     20   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                   Contact angle (°)                                                              114                                                                              120 119 121                                                                (56)                                                                             (67)                                                                              (82)                                                                              (68)                                                       Eluting potential                                                                     1.6                                                                              1.9 1.9 1.5                                                        (V vs SCE)                                                                            (1.4)                                                                            (-0.2)                                                                            (1.5)                                                                             (0.3)                                     21   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                  Contact angle (°)                                                              116                                                                              121 120 120                                                                (56)                                                                             (67)                                                                              (82)                                                                              (68)                                                       Eluting potential                                                                     1.6                                                                              1.9 1.9 1.6                                                        (V vs SCE)                                                                            (1.4)                                                                            (-0.2)                                                                            (1.5)                                                                             (0.3)                                     22   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                   Contact angle (°)                                                              112                                                                              120 121 120                                                                (56)                                                                             (67)                                                                              (82)                                                                              (68)                                                       Eluting potential                                                                     1.6                                                                              1.9 1.9 1                                                          (V vs SCE)                                                                            (1.4)                                                                            (-0.2)                                                                            (1.5)                                                                             (0.3)                                     Compar-                                                                            CF.sub.3 (CF.sub.2).sub.6 C.sub.6 H.sub.4 NH--                                            Contact angle (°)                                                              90 114 110 106                                       ative                    (56)                                                                             (67)                                                                              (82)                                                                              (68)                                      example          Eluting potential                                                                     1.4                                                                              0.2 1.6 0.5                                                        (V vs SCE)                                                                            (1.4)                                                                            (-0.2)                                                                            (1.5)                                                                             (0.3)                                     __________________________________________________________________________

EXAMPLES 23-26

Tribological Treatment

An Na salt of each 6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiolshown in Table 7 below was dissolved in an ordinarily used water basedlubricant (an emulsion type lubricant comprising of extreme pressureinhibitor, oiliness improver, emulsifying agent, forming inhibitor andthe like) at a concentration of 5×10⁻³ mol/L and used as the lubricant.A circular cutting of a metal column (30×30 φmm) was conducted with useof an engine lathe (emcomat-7 manufactured by Austria Mayer Co. Ltd.) ata rate of 1450 rpm, while poring the above-prepared lubricant at a rateof 3 cm³ /min. The cuttings obtained during the machining were gatheredto amount to 2 g. The cuttings were well washed with water and methanol,and then dried. The thus-obtained cuttings were dipped in 20 ml of THFfor 12 hours at a temperature of 40° C., so that the compounds which hadadhered to the surface of the cuttings were dissolved therein. Themolecular weight as well as the amount of film of respective dissolvedcompounds were measured with use of GPC (gel permeation chromatograph).The results are also shown in Table 7. The molecular weight measured inthe comparative example shows that the dissolved compound was a dimer ora trimer, while each molecular weight measured in the examples 23-26indicates that the dissolved compound was a considerably large polymer.The amount of film in the comparative example was very little andfurther, the amounts of film in the examples of the present inventionare lager than that in the comparative example by a hundred times ormore. The larger the molecular weight is, the higher the strength of thefilm. In addition, a larger amount of film means a more excellentcorrosion resistance.

                                      TABLE 7                                     __________________________________________________________________________    Tribological treatment of metals with use of                                  6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol                                                Number-average                                                                         Amount of film                                                       molecular weight                                                                       (μg/g)                                                            Iron Copper                                                                            Iron Copper                                       Example                                                                              Substituent in 6 place                                                                    column                                                                             column                                                                            column                                                                             column                                       __________________________________________________________________________    23     CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH--                                                   3,300                                                                              17,000                                                                            1.5  5.4                                          24     CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                   8,200                                                                              26,000                                                                            1.6  6.4                                          25     CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                  9,300                                                                              31,000                                                                            1.9  6.9                                          26     CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                   9,800                                                                              36,000                                                                            2.1  7.1                                          Comparative                                                                          CF.sub.3 (CF.sub.2).sub.6 C.sub.6 H.sub.4 NH--                                            1,500                                                                               3,200                                                                            <0.1 <0.1                                         example                                                                       __________________________________________________________________________

EXAMPLES 27-30

Electrolytic Polymerization Treatment

An Na salt of each 6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiolshown in Table 8 below was dissolved in water at a concentration of5×10⁻³ mol/L to prepare an electrolyte. The thus-obtained electrolytewas charged into an electrolytic cell (K. Mori:), and while using acathode of iron plate or SUS 304 plate (30×60×0.2 mm) and an anode ofplatinum plate, electrolytic polymerization was conducted for 10 minutesat a current density of 0.1 mA/cm² and a temperature of 40° C. Afterthis electrolytic polymerization, the iron plate and SUS 304 plate usedas the cathode were washed with methanol to remove unreacted substances,and then dried.

After that, the iron plate and SUS 304 plate were dipped in 20 ml of THFfor 12 hours at a temperature of 40° C., so that the compounds which hadadhered to the surface of each plate were dissolved therein. Themolecular weight as well as the amount of film of respective dissolvedcompounds were measured with use of GPC (gel permeation chromatograph).The results are also shown in Table 8. The examples of this inventionshow superior results in both number-average molecular weight and amountof film than the comparative example by ten to hundred times.Accordingly, it would be understood that the material structure of thepresent invention leads to a high reactivity.

                                      TABLE 8                                     __________________________________________________________________________    Electrolytic polymerization treatment of metals with use of                   6-perfluoro alkylamino-1,3,5-triazine-2,4-dithiol                                              Number-average                                                                          Amount of film                                                      molecular weight                                                                        (μg/cm.sup.2)                                                         SUS 304   SUS 304                                       Example                                                                            Substituent in 6 place                                                                    Iron plate                                                                         plate                                                                              Iron plate                                                                         plate                                         __________________________________________________________________________    27   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 NH--                                                   109,000                                                                            110,000                                                                            2.3  6.6                                           28   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.4 H.sub.7)N--                                   280,000                                                                            340,000                                                                            6.7  12.6                                          29   CF.sub.3 (CF.sub.2).sub.6 CH.sub.2 (C.sub.6 H.sub.11)N--                                  310,000                                                                            350,000                                                                            6.8  13.2                                          30   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 (C.sub.4 H.sub.7)N--                                   320,000                                                                            330,000                                                                            6.3  13.6                                          Compar-                                                                            CF.sub.3 (CF.sub.2).sub.6 C.sub.6 H.sub.4 NH--                                             9,800                                                                              12,000                                                                            0.3  0.6                                           tive                                                                          example                                                                       __________________________________________________________________________

As described above, the triazine thiol derivative having a perfluorogroup according to the present invention is excellent in reactivity,solubility and surface activity and thus, industrial fields and uses towhich the triazine thiol derivative having a perfluoro group of thepresent invention is applicable has been greatly enlarged. A film formetal surface formed of the triazine thiol derivative having a perfluorogroup according to the present invention has properties such ascorrosion resistance, lubricity, anti-staining property, nontackiness,anti-fogging property, anti-icing property and the like. Accordingly, itis applicable to various products which requires these properties (forinstance, materials for connector, metal gears, metal products fordecoration, metallic mirrors, metallic molds, hard discs, magnetictapes, hands of watch, metallic tableware and the like). Moreover, sincethe film of the triazine thiol derivative having a perfluoro groupaccording to the present invention has a surface of low free energy, itis effectively used in complexing with various fluoride, therebycontributing fluoridation of many metals and electric conductors.

Although the invention has been described with reference to specificpreferred embodiments, they were given by way of examples only and thus,it should be noted that various changes and modifications may be made onthem without departing from the scope of the present invention asdefined by the appended claims.

What is claimed is:
 1. A triazine thiol derivative having a perfluorogroup represented by the following chemical formula (1): ##STR10##wherein "n" is an integer of 1-12, "R" is represented by the followinggeneral formula;

    C.sub.m H.sub.2m+1

wherein m is an integer of 0-24, and M₁ and M₂ respectively represent ahydrogen atom (H) or an alkali metal.
 2. A method for producing atriazine thiol derivative having a perfluoro group comprisingpreparation steps of:(1) synthesizing a secondary amine having aperfluoro group; (2) synthesizing a triazine dichloride having aperfluoro group from said secondary amine having a perfluoro group andcyanur chloride; and then (3) synthesizing a triazine thiol derivativehaving a perfluoro group from said triazine dichloride having aperfluoro group.
 3. A method for producing a triazine thiol derivativehaving a perfluoro group comprising preparation steps of:(1)synthesizing a secondary amine having a perfluoro group, wherein saidsecondary amine having a perfluoro group is prepared through a reactionrepresented by the following reaction formula; ##STR11## wherein R isdefined as in claim 1 (2) synthesizing a triazine dichloride having aperfluoro group from said secondary amine having a perfluoro group andcyanur chloride, said triazine dichloride having a perfluoro group isprepared through a reaction represented by the following reactionformula; ##STR12## and then (3) synthesizing a triazine thiol derivativehaving a perfluoro group from said triazine dichloride having aperfluoro group, said triazine thiol derivative having a perfluoro groupis prepared through a reaction represented by the following reactionformula; ##STR13## wherein R is defined as in claim
 1. 4. A film formetal surface comprising a triazine thiol derivative having a perfluorogroup as set forth in claim 1.